US6027808A - Cemented carbide for a drill, and for a drill forming holes in printed circuit boards which is made of the cemented carbide - Google Patents
Cemented carbide for a drill, and for a drill forming holes in printed circuit boards which is made of the cemented carbide Download PDFInfo
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- US6027808A US6027808A US08/879,789 US87978997A US6027808A US 6027808 A US6027808 A US 6027808A US 87978997 A US87978997 A US 87978997A US 6027808 A US6027808 A US 6027808A
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- cemented carbide
- drill
- interior
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F7/00—Manufacture of composite layers, workpieces, or articles, comprising metallic powder, by sintering the powder, with or without compacting wherein at least one part is obtained by sintering or compression
- B22F7/008—Manufacture of composite layers, workpieces, or articles, comprising metallic powder, by sintering the powder, with or without compacting wherein at least one part is obtained by sintering or compression characterised by the composition
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/25—Web or sheet containing structurally defined element or component and including a second component containing structurally defined particles
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/25—Web or sheet containing structurally defined element or component and including a second component containing structurally defined particles
- Y10T428/252—Glass or ceramic [i.e., fired or glazed clay, cement, etc.] [porcelain, quartz, etc.]
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/30—Self-sustaining carbon mass or layer with impregnant or other layer
Definitions
- the present invention relates to a cemented carbide useful as a material for drills whose surface is coated with a coating of hard carbon such as diamond, non-crystalline diamond etc. and which are used for forming small diameter holes in printed circuit boards (hereafter referred to as PCB drills); and to the above-described kind of PCB drill itself.
- the cemented carbide to which the present invention is directed can be one in which the component which forms the binder phase is not limited to Co but may also be another metal from the iron group such as nickel.
- the present invention shall be hereunder explained taking Co as a representative example of the component which forms the binder phase.
- Printed circuit boards are made by binding glass fibers with epoxy resin and then attaching a film of copper on the surface thereof.
- printed circuit boards are being made with higher and higher density and consisting of more and more layers. Accordingly, there has been a demand that a material for a PCB drill to drill small diameter holes has wear resistance and breakage resistance significantly higher than conventional materials.
- WC-Co cemented carbides are generally used as materials for PCB drills.
- the hardness can be increased without decreasing the toughness, by reducing the size of the WC grains. From this standpoint, the cemented carbides disclosed in Japanese Patent Application Publication No. Sho 61-12847 and Japanese Patent Application Publication No. Sho 61-195951 have been proposed.
- V and Cr WC grain growth inhibitors
- a WC-Co cemented carbide or WC-Ni cemented carbide
- a cemented carbide having excellent wear resistance and toughness and having a dispersed phase of fine WC grains which have an average grain size of 0.7 ⁇ m or less can be obtained.
- HRC Rockwell hardness
- Ta, Mo etc. are also known as elements for WC grain growth inhibitors (for example, see "Powders and Powder Metallurgy" 19(1972) p. 67).
- hard carbons such as diamond, non-crystalline diamond etc.
- hard carbon coated cemented carbide tools comprising a base material made of an ultra-fine grade cemented carbide having excellent toughness and a coating of hard carbon formed thereon by chemical vapor deposition.
- the cemented carbides include about 3 to 20% of iron group elements such as Co, Ni etc., and the carbon dissolves into the binder phase during synthesis of the hard carbon coating whereby a hard film cannot be formed, or even if a hard film is partially formed, the adhesion thereof to the cemented carbide base material is not sufficient whereby the coating easily becomes peeled from the base material.
- the present invention was made in the light of this state of the art, and has as its objective the provision of a cemented carbide for a drill which has excellent anti-breakage resistance and which exhibits good adhesion when coated with a hard carbon coating. It also has as its objective the provision of a drill for forming small diameter holes in printed circuit boards which is made of this cemented carbide.
- the cemented carbide of the present invention which achieves these objectives is a WC-iron group metal cemented carbide which has as its main component WC having an average grain size of 0.7 ⁇ m or less; contains 0.1 to 3.0 weight percent of at least one type of element selected from the group of V, Cr, Ta and Mo; whose surface layer consists of substantially only WC or WC grains and components other than binder phase comprising iron group metals; wherein the average particle size of the WC in the surface layer is larger than the average grain size of the WC in the interior; and wherein the Young's Modulus of the interior of said cemented carbide is 600 MPa or more.
- a typical example of a cemented carbide of the present invention is one having Co as the iron group metal.
- V be included in a weight ratio in the range of 0.015 to 0.032 with respect to the iron group metal used as the binder-phase forming component.
- cemented carbide of the present invention is exhibited to its maximum when the above-described cemented carbide of the present invention is coated with a hard carbon coating and used as a material of a PCB drill having a cutting point diameter of 0.30 to 0.50 mm.
- FIG. 1 is a graph showing the effect on the breakage of the drill of changes in the cutting resistance accompanying an increase in the number of drilling.
- the inventors of the present invention carried out investigations into the changes in the cutting resistance accompanying an increase in the number of hits (number of times drill was used to form a hole), when holes are formed with a fine diameter PCB drill coated with a hard carbon coating, and having a cutting point diameter of ⁇ 0.5 mm or less, and compared the results with the case when a PCB drill having no hard carbon coating was used to form holes.
- the results are shown schematically in FIG. 1, and from these results the following inferences were made.
- the inventors of the present invention carried out studies into cemented carbides which have excellent breakage resistance and excellent adhesion (with the hard carbon coating) when a hard carbon coating is formed on the surface thereof by chemical vapor deposition; and into the surface state of such cemented carbides.
- a cemented carbide which (i) has as its main component WC having an average grain size of 0.7 ⁇ m or less; (ii) includes 0.1 to 3.0 weight percent of one or more elements selected from the group of V, Cr, Ta and Mo; (iii) has had its surface modified in the way described hereunder; and (iv) has a Young's Modulus higher than a specific value, could be used to obtain a hard-carbon coated PCB drill which displays excellent properties with respect to the adhesion between the cemented carbide and the hard carbon coating and which displays excellent breakage resistance even after the formation of the hard-carbon coating.
- the state of the modified surface of the cemented carbide here is one in which (A) the surface layer is consists of substantially only WC or only WC grains and components other than binder phase comprising iron group metals; and (B) the average grain size of the WC in the surface layer is even larger than the average grain size of the WC in the interior, etc.
- Methods for modifying the surface of the cemented carbide in the above-mentioned way include heat treatment methods in which the outermost surface layer of the cemented carbide has its temperature raised to a temperature equal to or higher than the temperature at which the metal binder phase starts to melt.
- Such methods include those disclosed in for example Japanese Patent Application Publication No. Hei 7-11375 such as high frequency heating in a hydrogen atmosphere, exposure treatment in an atmosphere gas plasma, or DC pulse discharge treatment in an inert gas atmosphere.
- the energy supplied per unit area to the outermost surface is even more than the energy supplied when the cemented carbide is sintered, and thus even with cemented carbides which have been treated at the time of sintering such that there is no WC grain growth, it is possible to effect recrystallization and produce coarse grains with respect to only those WC grains in the outermost surface layer.
- the Young's Modulus in the interior is 600 MPa or higher, and thus the bend of the drill during hole-boring is small. This has the effect of suppressing the speed at which microcracks in the surface of the cemented carbide base material made brittle by the modifying treatment reach a size at which they become the cause of breakage of the drill itself, and as a result, a PCB drill cemented carbide having excellent breakage resistance can be obtained.
- vanadium is precipitated as (W,V)C in such a manner that it fills the gaps formed between the WC grains in the surface layer of the base material by the surface modifying treatment, and acts to suppress the diffusion of iron group metals from the interior of the cemented carbide to the surface of the cemented carbide during the hard carbon coating. It is thereby possible to maintain an excellent level of adhesion between the cemented carbide and the hard carbon coating.
- V exhibits the above-described kind of effect is not completely understood, but the following can probably be considered to be the reason.
- the amount of V which solidly dissolves in the iron group metal phase in the form of solid solution (for example, Co) is small compared to other WC grain growth inhibitors, and most of the V added does not dissolve in the binder phase but becomes precipitated in the form of (W,V)C. Furthermore, the precipitated form of the (W,V)C is similar to the precipitated form of the binder phase.
- the (W,V)C can become precipitated in such a way that it fills the gaps formed between the WC grains, and it is thought that it acts as a barrier which suppresses the diffusion of iron group metals from the interior of the cemented carbide to the surface of the cemented carbide during the subsequent step of forming the hard carbon coating.
- the reasons for the limits for the features of the cemented carbide (for a drill) of the present invention shall be explained.
- the cemented carbide (for a drill) of the present invention have a Young's Modulus which is 600 MPa or higher. If the Young's Modulus is lower than 600 MPa, it is impossible to suppress the speed at which microcracks in the surface of the cemented carbide base material made brittle due to the modifying treatment grow to a size at which they cause breakage of the drill itself. It is preferred that the Young's Modulus be 610 MPa or higher.
- the Young's Modulus of the cemented carbide is mainly fixed by the composition of the cemented carbide.
- the content of WC grain growth inhibitors such as V, Cr, Ta and Mo is in the range of 0.1 to 3.0 weight percent as in the present invention, the Co content should be adjusted to 7 weight percent or less in order to make the Young's Modulus of the cemented carbide equal to 600 MPa or higher.
- the above-mentioned WC grain growth inhibitors are generally added in the form of carbides, and these generally exist in the cemented carbide in their original carbide form or in the form of a solid solution.
- Zr is also known as a WC grain growth inhibitors, but due to the fact that the addition of Zr can cause a deterioration in the sinterability and consequent striking reduction in the bending strength of the cemented carbide, it cannot be used for the cemented carbide in the present invention.
- V be included in a weight ratio in the range of 0.015 to 0.032 with respect to the iron group metals. If the weight ratio is less than 0.015, there is almost no precipitation of (W,V)C between the WC in the surface layer of the base material at the time of surface modifying, with a consequent reduction in the effect of suppressing the diffusion of iron group metals from the interior of the cemented carbide to the surface of the cemented carbide when forming the hard carbon coating.
- the basic structure of the cemented carbide used in the present invention is one in which the average grain size of the WC in the interior thereof is 0.7 ⁇ m or less. If this average grain size exceeds 0.7 ⁇ m, then the desired anti-breakage properties for the cemented carbide base material itself cannot be obtained. Furthermore, the cemented carbide of the present invention includes 0.1 to 3.0 weight percent of V, Cr, Ta, Mo etc. These components have the effect of suppressing the growth of the WC grains as mentioned above, and if their content is less than 0.1 weight percent, this effect is not sufficiently exhibited. If the content exceeds 3.0 weight percent, the carbides and solid solutions become coarse causing a reduction in the toughness and strength.
- a PCB drill made by coating the above-described cemented carbide of the present invention with a hard carbon coating, and having a cutting point diameter in the range of 0.30 to 0.50 mm exhibits a performance superior to that of conventional PCB drills.
- the cemented carbide of the present invention is not limited to ones having Co as the binder-phase forming component but may also include other iron group metals such as Ni.
- Ni instead of Co can cause a striking reduction in the bending strength of the cemented carbide, and thus when Ni is used, it is preferred that it is used to replace a portion of the Co to the extent that there is no remarkable reduction of the bending strength.
- WC having an average grain size of 0.4 ⁇ m or 0.5 ⁇ m
- Co having an average grain size of 1.3 ⁇ m
- VC having an average grain size of 1.3 ⁇ m
- Cr 3 C 2 having an average grain size of 1.0 ⁇ m
- Mo 2 C having an average grain size of 2.0 ⁇ m
- the mixture of powder raw materials was then mixed for 8 hours in an organic solvent using an attrition ball mill. This was followed by the addition of paraffin and drying. The dried mixture was then shaped by powder pressing at 100 MPa, followed by dewaxing and preliminary sintering. The pre-sintered product was then machine-cut into the required shape, followed by vacuum sintering for 1 hour at 1400° C. It was then subject to HIP treatment for 1 hour in an atmosphere of Ar at 100 MPa and 1350° C. to obtain the base material for a drill. The thus obtained base material had the properties shown in Table 2.
- the drill base materials A to D were used to make PCB drill materials A to D (cutting point diameter: 0.40 mm). These PCB drill materials were treated for 5 minutes in a hydrogen plasma atmosphere, which was made by exciting hydrogen gas with microwaves, in such a way that only the tip reached a surface temperature of 1300° C., followed by further treatment for 2 minutes in a hydrogen/methane plasma, made by adding 0.2 volume percent of methane gas to the hydrogen gas.
- the PCB drill materials A to D obtained in this way were adopted as inventive examples 1 and 2 and comparative examples 1 and 2 respectively.
- the distribution of Co in the surface and the average grain size of the WC grains in the surface layer after treatment were studied by electron probe microanalysis (EPMA) and scanning electron microscope (SEM) analysis. The results thereof are shown in Table 3.
- the PCB drill materials A to D which had been subjected to plasma treatment were immersed in a suspension of abrasive diamond grains (average grain size of about 0.3 ⁇ m) dispersed in ethanol, and then subjected to ultrasonic treatment.
- a hard carbon coating of a thickness of about 8.5 ⁇ m was then formed on the cutting point portion thereof by chemical vapor deposition for 7 hours with an excited methane-hydrogen gas mixture using a microwave plasma CVD method, to obtain 4 types of hard-carbon coated PCB drills.
- the conditions of synthesis were as follows:
- Drill material temperature 800° C.
- Methane concentration 2.5 volume percent.
- the hard-carbon coated PCB drills of inventive examples 1 and 2 and comparative examples 1 and 2 were then used in a test in which holes were bored in a printed circuit boards.
- the cutting conditions were as follows:
- Work material 3 layer stack of glass-epoxy resin boards each having a thickness of 1.6 mm; Rotation speed: 80000 rpm; Feed rate: 2.8 m/min.
- the drill base materials A, B, E and F of Table 1 were used to produce PCB drill base materials A, B, E and F (cutting point diameter: 0.35 mm). These PCB drill base materials A, B, E, F were treated for 5 minutes in a plasma atmosphere, which was made by exciting hydrogen gas with microwaves, in such a way that only the tip reached a surface temperature of 1300° C., followed by further treatment for 2 minutes in a hydrogen/methane plasma, made by adding 0.2 volume percent of methane gas to the hydrogen gas.
- the PCB drill materials A, B, E and F obtained in this way were adopted as inventive examples 3, 4, 5 and 6 respectively.
- the distribution of Co in the surface and the average grain size of the WC grains in the surface layer after treatment were studied by electron probe microanalysis (EPMA) and scanning electron microscope (SEM) analysis. The results thereof are shown in Table 4.
- the PCB drill materials A, B, E and F which had been subjected to plasma treatment were immersed in a suspension of abrasive diamond grains (average grain size of about 0.3 ⁇ m) dispersed in ethanol, and then subjected to ultrasonic treatment.
- a hard carbon coating of a thickness of about 7.5 ⁇ m was formed on the cutting point portion thereof by chemical vapor deposition for 7 hours with an excited methane-hydrogen gas mixture using a microwave plasma CVD method, to obtain 4 types of hard-carbon coated PCB drills.
- the conditions of synthesis were as follows:
- Drill material temperature 800° C.
- Methane concentration 2.0 volume percent.
- Work material 2 layer stack of glass-epoxy resin boards each having a thickness of 1.6 mm; Rotation speed: 75000 rpm; Feed rate: 2.4 m/min.
- inventive example 6 the content of vanadium with respect to the Co in the drill base material had the high value of 0.036, and it is thought that this suppressed the growth of WC grains due to WC recrystallization in the outermost surface of the base material at the time of surface modifying, with the result that the gaps due to volatilization of Co existed between the grains in the outermost surface layer; which caused a reduction in the strength of the outermost surface layer of the base material and consequent flaking of the coating from the outermost surface layer of the base material.
- inventive examples 3 and 4 which contained an appropriate amount of vanadium, there was no flaking of the coating and the shape of the bored holes was excellent even after 50000 hits.
- the present invention has the construction described above, and makes it possible to produce (i) a cemented carbide for a hard-carbon coated PCB drill which has excellent breakage resistance and which displays good adhesion when coated with a hard-carbon coating, and (ii) a hard-carbon coated PCB drill having excellent breakage resistance which is made using said cemented carbide; and the present invention can thus be expected to one of extremely high industrial value.
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Abstract
Description
TABLE 1 __________________________________________________________________________ Composition Drill VC Cr.sub.3 C.sub.2 TaC Mo.sub.2 C WC WC Weight ratio Material Co (in terms of V) (in terms of Cr) (in terms of Ta) (in terms of Mo) (AVGD: 0.5 μm) (AVGD: 0.4 of V w.r.t __________________________________________________________________________ Co A 5.0 0.15 0.5 0 0.5 Rest -- 0.024 (0.12) (0.43) (0.47) B 5.5 0.10 0.5 0.25 0 -- Rest 0.015 (0.08) (0.43) (0.23) C 9.0 0.30 1.0 0 0 Rest -- 0.027 (0.24) (0.87) D 12.0 0.35 1.0 0 0.8 Rest -- 0.024 (0.28) (0.87) (0.75) E 5.0 0 0.5 0.3 0 -- Rest 0 (0.43) (0.28) F 5.5 0.25 0.5 0 0 Rest -- 0.036 (0.207) (0.43) __________________________________________________________________________ Note: AVGD is an abbreviation for average grain diameter.
TABLE 2 ______________________________________ Drill AVGD of WC grains Young's Modulus Transverse Rupture Material in interior (MPa) (GPa) ______________________________________ A 0.6 625 4.0 B 0.5 620 4.1 C 0.6 582 4.0 D 0.6 560 4.3 E 0.7 625 3.9 F 0.6 617 4.0 ______________________________________
TABLE 3 ______________________________________ AVGD of WC Drill grains in surface Co remaining in Material layer surface layer ______________________________________ Inventive Example 1 A 1.1 None Inventive Example 2 B 1.2 None Comp. Example 1 C 1.1 None Comp. Example 2 D 1.1 None ______________________________________
TABLE 4 ______________________________________ AVGD of WC Drill grains in surface Co remaining in Material layer surface layer ______________________________________ Inventive Example 3 A 1.1 None Inventive Example 4 B 1.2 None Inventive Example 5 E 1.3 None Inventive Example 6 F 0.8 None ______________________________________
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Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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JP8299085A JPH10138027A (en) | 1996-11-11 | 1996-11-11 | Cemented carbide for drill and drill for printed board drilling using same cemented carbide |
JP8-299085 | 1996-11-11 |
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US6027808A true US6027808A (en) | 2000-02-22 |
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US08/879,789 Expired - Lifetime US6027808A (en) | 1996-11-11 | 1997-06-20 | Cemented carbide for a drill, and for a drill forming holes in printed circuit boards which is made of the cemented carbide |
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Cited By (13)
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US6220797B1 (en) * | 1998-06-18 | 2001-04-24 | Sumitomo Metal Minning Co. | Surface treated steel cutting tool |
WO2003010350A1 (en) | 2001-07-23 | 2003-02-06 | Kennametal Inc. | Fine grained sintered cemented carbide, process for manufacturing and use thereof |
US20030118412A1 (en) * | 2001-12-26 | 2003-06-26 | Sumitomo Electric Industries, Ltd. | Surface-coated machining tools |
US6660329B2 (en) | 2001-09-05 | 2003-12-09 | Kennametal Inc. | Method for making diamond coated cutting tool |
US20040009088A1 (en) * | 2002-04-17 | 2004-01-15 | Johannes Glatzle | Hard metal component with a graduated structure and methods of producing the component |
US20040141867A1 (en) * | 2001-05-16 | 2004-07-22 | Klaus Dreyer | Composite material and method for production thereof |
US6843824B2 (en) * | 2001-11-06 | 2005-01-18 | Cerbide | Method of making a ceramic body of densified tungsten carbide |
US20050039574A1 (en) * | 2002-10-25 | 2005-02-24 | Sandvik Ab | Cemented carbide for oil and gas applications with toughness factor |
US20070009764A1 (en) * | 2005-06-27 | 2007-01-11 | Sandvik Intellectual Property Ab | Fine grained sintered cemented carbides containing a gradient zone |
US20070148497A1 (en) * | 2005-12-16 | 2007-06-28 | Sandvik Intellectual Property Ab | Coated cutting tool insert |
US20150016908A1 (en) * | 2012-02-28 | 2015-01-15 | Kyocera Corporation | Drill blank, method for manufacturing drill blank, drill, and method for manufacturing drill |
US9228252B2 (en) | 2011-06-27 | 2016-01-05 | Kyocera Corporation | Hard alloy and cutting tool |
US11821062B2 (en) | 2019-04-29 | 2023-11-21 | Kennametal Inc. | Cemented carbide compositions and applications thereof |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
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JP4349384B2 (en) * | 2005-07-25 | 2009-10-21 | 三菱マテリアル株式会社 | Micromachining tool and brittle material micromachining method |
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